CN100593511C - Method for preparing carbon nano-tube and carbon nano-fibre by using phenol resin as carbon source - Google Patents
Method for preparing carbon nano-tube and carbon nano-fibre by using phenol resin as carbon source Download PDFInfo
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- CN100593511C CN100593511C CN200710160201A CN200710160201A CN100593511C CN 100593511 C CN100593511 C CN 100593511C CN 200710160201 A CN200710160201 A CN 200710160201A CN 200710160201 A CN200710160201 A CN 200710160201A CN 100593511 C CN100593511 C CN 100593511C
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Abstract
The invention relates to a method for preparing carbon nanotubes and carbon nanofiber with phenolic resin as the carbon source. The method includes the following steps: preparing 10wt % aqueous solution from 1-3wt% based on base material weight into the nickel nitrate, and mixing with the base material which is at least one out of alumina powder and crystalline flake graphite and baked to remove the moisture; adding 3-15wt% phenolic resin to the base material mixed with nickel nitrate catalyst, mixing, and pressing under a pressure of 100-200MPa to obtain the lump material; drying into a drying oven until moisture content reaches 1.0-2.0wt%, carbon burial heating in a resistance furnace up to 1,200-1,450 DEG C and holding for 4-5 hours, and cooling to 0-45 DEG C to grow carbon nanotubes orcarbon nanofiber on the alumina and graphite substrate. The method has the advantages that the preparation method and process are simple and the processing parameters are easily controlled; carbon source for preparing carbon nanotubes and carbon nanofiber adopts the phenolic resin as the bonding agent for refractory material with low cost and easy accessibility; and the obtained carbon nanotubesand carbon nanofiber have large quantity, diameter of 50-400m, length of tens of micrometers, and clear hollow structure as displayed in scanning electron microscope photos, and grow on the substratematerial with a bundle shape with good growth condition.
Description
Technical field
The present invention relates to the technology of preparing of a kind of carbon nanotube and carbon nanofiber, particularly a kind ofly do the method that carbon source prepares carbon nanotube and carbon nanofiber with resol.
Background technology
Carbon nanotube and carbon nanofiber are because its particular structure and performance are the focuses of Recent study always.In the preparation research of numerous carbon nanotubes and carbon nanofiber, the selection of carbon source and use are bases and crucial.Carbon nanotube or carbon nanofiber can obtain from the pyrolysis or the conversion of various carbon sources.The carbon source of using is mainly the carbonaceous gas carbon source at present, is mainly acetylene, methane, ethene, propylene, butylene, benzene and normal hexane etc.The method of making carbon source manufacturing carbon nanotube and carbon nanofiber with carbonaceous gas is called chemical Vapor deposition process.The main processes of this method under certain process conditions with the carbonaceous gas carbon source: acetylene, methane, ethene, propylene, butylene, benzene and normal hexane etc. are passed in the container of laying body material or collection device with protection gas and catalyzer vapour; or earlier with catalyzer attached on the body material; feed carbon-source gas and protection gas again; the deposition of RESEARCH OF PYROCARBON on body material or collection device by catalyst pyrolysis carbonaceous gas carbon source obtains obtains carbon nanotube and carbon nanofiber.Make of carbonaceous gas that carbon source prepares carbon nanotube and the carbon nanofiber common drawback is the manufacturing cost height, the preparation condition harshness, gaseous carbon sources CONTROL PROCESS complexity in the preparation process, product production is low, is difficult to realize large-scale industrial production.Obtaining many, well-grown carbon nanotubes of quantity and carbon nanofiber as how simple preparation technology, cheap raw material, is to need the problem that solves in carbon current nanotube and the carbon nanofiber technology of preparing.
Summary of the invention
The purpose of this invention is to provide that a kind of preparation method who is used to prepare carbon nanotube and carbon nanofiber is easy, technological process is simple, every processing parameter is easy to control, carbon source is easy to obtain and cheap, prepared carbon nanotube and carbon nanofiber quantity are many, be from the shape growth on body material, well-grownly do the method that carbon source prepares carbon nanotube and carbon nanofiber with resol.
Preparation method of the present invention is: with resol make carbon source, with aluminum oxide powder and crystalline flake graphite as the body material of carbon nanotube and carbon nanofibers grow, with the catalyzer of nickelous nitrate as carbon nanotube and carbon nanofibers grow, concrete preparation process is: will account for the body material weight percent and be 1～3% nickelous nitrate be mixed with mass percentage concentration be behind 10% aqueous solution with the body material thorough mixing, body material is at least a in aluminum oxide powder and the crystalline flake graphite, and mixture is dried to remove moisture wherein; To account for body material weight percent 3～15% resol then and join in these body materials that are mixed with the catalyzer nickelous nitrate, behind the thorough mixing mixture will be pressed into lumpy material under the pressure of 100～200MPa; With the lumpy material after the moulding place loft drier dry to moisture content be 1.0-2.0wt%, in resistance furnace, bury carbon and be heated to 1200 ℃～1450 ℃, be incubated after 4～5 hours, be cooled between 0 ℃ to 45 ℃, can on aluminum oxide and/or graphite matrix, grow carbon nanotube and carbon nanofiber.
Effect of the present invention is: carbon nanotube and carbon nanofiber preparation method are easy among the present invention, and technological process is simple, and every processing parameter is easy to control; The carbon source that is used to prepare carbon nanotube and carbon nanofiber is a refractory binder resol, and is cheap and be easy to obtain; Prepared carbon nanotube and carbon nanofiber quantity are many, are on body material from the shape growth, and well-grown, diameter are 50nm～400nm, and length can reach tens of microns, and stereoscan photograph has shown its hollow structure clearly.The present invention has overcome with gas and has prepared the deficiency that exists in carbon nanotube and the carbon nanofiber technology as carbon source, for carbon nanotube and carbon nanofiber technology of preparing provide new method and thinking.
Description of drawings
Fig. 1 has the pictorial diagram of the body material of carbon nanotube and carbon nanofiber for growth among the present invention;
Fig. 2 is the carbon nanotube that makes among the present invention and the sem photograph of carbon nanofiber;
Fig. 3 is carbon nanotube and carbon nanofiber energy spectrum composition analysis collection of illustrative plates among the present invention.
Embodiment
Embodiment
Table 1 raw material physical and chemical index
| Material name | Resol | Nickelous nitrate | Aluminum oxide | Crystalline flake graphite |
| Main physical and chemical index | Transparent brown liquid, solids content 70～80%, density 1.18～1.22g/cm 3, free phenol 10～20%, fixed carbon 43～49%, moisture＜10%. | Analytical pure, blue-greenish colour crystal, Ni (NO 3) 2.6H 2O content 〉=98%, water-insoluble≤0.005%. | Granularity＜0.5mm, Al 2O 3Content 〉=98% | Median size 0.27mm, fixed carbon 〉=96% |
Implementation step is as follows:
1. choose each raw material according to the physical and chemical index of raw material shown in the table 1.Take by weighing the aluminum oxide powder of 1Kg, to make mass percentage concentration be to add behind 10% aqueous solution in the aluminum oxide powder and thorough mixing with addition of going into 95g distilled water with the 15g nickelous nitrate;
2. mixture places 110 ℃ dry 48 hours generals of loft drier moisture wherein to get rid of, and desciccate is standby after 30 minutes in grinding in ball grinder;
3. taking by weighing 30g resol heats after 15 minutes in 80 ℃ water-bath and joins in the aluminum oxide powder ground in the step 2, thorough mixing is after 20 minutes in stirrer, mixture is pressed into volume density on universal press be 2.8 ± 0.1g/cm3, is of a size of the lumpy material of φ 50mm * 50mm;
4. the loft drier that the lumpy material after the moulding is placed 180 ℃ is imbedded in the saggar that the coke grain is housed after dry 24 hours, is heated to 1200 ℃ in resistance furnace, is incubated after 4 hours, naturally cools to room temperature.Product placed under the scanning electron microscope observe, promptly can observe and on alumina substrate, grow big, well-grown carbon nanotube of quantity and carbon nanofiber.
Embodiment 2
Implementation step is as follows:
1. choose each raw material according to the physical and chemical index of raw material shown in the table 1.Take by weighing the crystalline flake graphite of 1Kg, take by weighing the 20g nickelous nitrate and be dissolved in that to be mixed with mass percentage concentration in 180 distilled water be to add in the crystalline flake graphite behind 10% aqueous solution and thorough mixing; The moisture that mixture places 110 ℃ loft drier to incite somebody to action in dry 48 hours is wherein got rid of;
2. taking by weighing 150g resol heats after 15 minutes in 80 ℃ water-bath and joins in the above-mentioned crystalline flake graphite, thorough mixing is after 20 minutes in stirrer, it is 1.5 ± 0.1g/cm3 that mixture is pressed into volume density with universal press, is of a size of the lumpy material of φ 50mm * 50mm;
3. the loft drier that the lumpy material after the moulding is placed 180 ℃ is imbedded in the saggar that the coke grain is housed after dry 24 hours, is heated to 1300 ℃ in resistance furnace, is incubated after 4 hours, naturally cools to room temperature.Product placed under the scanning electron microscope observe, promptly can observe in the graphite matrix surface growth and go out big, well-grown carbon nanotube of quantity and carbon nanofiber.
Embodiment 3
Implementation step is as follows:
1. choose each raw material according to the physical and chemical index of raw material shown in the table 1.Take by weighing aluminum oxide powder and the 200g crystalline flake graphite thorough mixing of 800g, the 30g nickelous nitrate is dissolved in to be mixed with mass percentage concentration in the 270g distilled water be to join in the mixture of aluminum oxide powder and crystalline flake graphite behind 10% aqueous solution, and thorough mixing is even;
2. mixture is placed 110 ℃ loft drier that moisture is wherein got rid of, and desciccate is standby after 30 minutes in grinding in ball grinder;
3. taking by weighing 80g resol heats after 15 minutes in 80 ℃ water-bath and joins in the above-mentioned desciccate, thorough mixing is after 20 minutes in stirrer, it is 2.5 ± 0.1g/cm3 that mixture is pressed into volume density with universal press, is of a size of the lumpy material of φ 50mm * 50mm;
4. the loft drier that the lumpy material after the moulding is placed 180 ℃ is imbedded in the saggar that the coke grain is housed after dry 24 hours, is heated to 1450 ℃ in resistance furnace, is incubated after 4 hours, naturally cools to room temperature.Product placed under the scanning electron microscope observe, promptly can observe at aluminum oxide powder and graphite matrix surface growth and go out big, well-grown carbon nanotube of quantity and carbon nanofiber.
Claims (1)
1. do the method that carbon source prepares carbon nanotube and carbon nanofiber with resol for one kind, it is characterized in that: will account for the body material weight percent and be 1～3% nickelous nitrate be mixed with mass percentage concentration be behind 10% aqueous solution with the body material thorough mixing, body material is at least a in aluminum oxide powder and the crystalline flake graphite, and it is dried to remove moisture wherein; To account for body material weight percent 3～15% resol then and join in these body materials that are mixed with the catalyzer nickelous nitrate, behind the thorough mixing mixture will be pressed into lumpy material under the pressure of 100～200MPa; With the lumpy material after the moulding place loft drier dry to moisture content be 1.0-2.0wt%, in resistance furnace, bury carbon and be heated to 1200 ℃～1450 ℃, be incubated after 4～5 hours, be cooled between 0 ℃ to 45 ℃, can on aluminum oxide and/or graphite matrix, grow carbon nanotube and carbon nanofiber.
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| Application Number | Priority Date | Filing Date | Title |
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| CN200710160201A CN100593511C (en) | 2007-12-14 | 2007-12-14 | Method for preparing carbon nano-tube and carbon nano-fibre by using phenol resin as carbon source |
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| CN200710160201A CN100593511C (en) | 2007-12-14 | 2007-12-14 | Method for preparing carbon nano-tube and carbon nano-fibre by using phenol resin as carbon source |
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| CN102530915A (en) * | 2011-12-23 | 2012-07-04 | 中钢集团洛阳耐火材料研究院有限公司 | Method for improving phenolic resin carbonized structure |
| CN102677193A (en) * | 2012-05-03 | 2012-09-19 | 东华大学 | Preparation method of phenolic resin matrix nano activated carbon fiber material |
| CN103072969A (en) * | 2013-01-29 | 2013-05-01 | 浙江大学 | Preparation method of grass-shaped carbon nanobelt |
| CN104600307B (en) * | 2015-01-13 | 2017-02-08 | 上海交通大学 | Preparation method of multiwalled carbon nanotube for lithium air battery positive electrode |
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| CN110330319A (en) * | 2019-07-13 | 2019-10-15 | 南昌航空大学 | A kind of aluminium carbon firing refractory material of low-carbon Ultra-low carbon and preparation method thereof |
| CN110240466A (en) * | 2019-07-13 | 2019-09-17 | 南昌航空大学 | A kind of low-carbon Ultra-low carbon carbon containing refractory and preparation method thereof combined containing the micro-nano graphite flake phenolic resin of two dimension removed in situ |
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| CN112408364B (en) * | 2020-11-30 | 2023-01-24 | 青岛科技大学 | Method for preparing carbon nano tube by catalytic pyrolysis of waste thermosetting plastic |
| CN117383949B (en) * | 2023-11-10 | 2024-04-02 | 江苏君耀耐磨耐火材料有限公司 | Preparation method of carbon nanofiber toughened refractory material |
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